Radiation-cured rubber-based pressure-sensitive adhesive

ABSTRACT

Polythiol crosslinking agents are used in combination with electron beam and/or photoinitiator ultraviolet cure to enhance the high temperature shear properties of rubber-based pressure-sensitive adhesives.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a continuation of application Ser. No. 06/896,127 filed Aug. 12, 1986, now U.S. Pat. No. 4,820,746.

BACKGROUND OF THE INVENTION

It is stated in U.S. Pat. No. 4,152,231 to St. Claire et al that adhesives based on hydrogenated monoalkenylarene-diene block copolymers have relatively low service temperature, poor ultraviolet resistance, poor solvent resistance and high viscosity.

It was proposed in the '231 patent that a composition based on 100 parts by weight linear or radially conjugated diene polymers which are homopolymers of C4 to C12 conjugated dienes and copolymers with two or more C4 to C12 conjugated dienes and their halogenated derivatives tackified with from 0 to 254 parts by weight tackifier resin could be enhanced with respect to shear strength, UV resistance and solvent resistance by radiation curing in the presence of 1 to 100 parts by weight di to tetra-functional acrylate or methacrylate selected from acrylic and methacrylic esters of polyols. Conventional plasticizer compounds, oils, liquid resins, fillers and anti-oxidants and the like could be tolerated.

The compositions were disclosed to be curable by exposure to high-energy radiation such as electron-beam (EB) radiation or ultraviolet (UV) radiation. Electron-beam was stated to be preferred since it enabled crosslinking of compositions based on either unhydrogenated or hydrogenated polymers while UV radiation could only initiate crosslinking with unhydrogenated polymers.

A photosensitizer is disclosed as necessary to speed ultraviolet crosslinking reactions.

Polythiols have been proposed for use in the polymerization of and/or crosslinking of polyols. Applications have ranged from the production of printing plates, photoresists, plastic bottle coatings, lacquers, cured elastomers and natural rubbers, water-coating and other compositions.

U.S. Pat. No. 3,920,877 to Barber et al discloses that the semi-solid pressure-sensitive polythiolether polymer systems may be formed by curing of liquid components using UV or beta radiation. The polymers are normally tacky and when fully cured are useful as pressure-sensitive adhesives. They are characterized as being comprised of liquid polyene compositions containing at least two unsaturated carbon to carbonyl bonds per molecule located terminally or pendant to the main chain backbone and cured to odorless tacky elastomer products with polyols under ambient conditions in the presence of a free-radical generator. The formed adhesives are useful for adhesive tapes, labels, tiles, coverings and the like.

SUMMARY OF THE INVENTION

There is provided in accordance with the invention radiation-curable and cured rubber-based pressure-sensitive adhesives which comprise at least one elastomeric rubber-based pressure-sensitive adhesive and, as a crosslinking agent, at least one polythiol, present in a total amount sufficient to increase upon exposure to electron-beam radiation and/or ultraviolet radiation, the latter with the further presence of a photoinitiator, the elevated temperature shear properties of said rubber-based pressure-sensitive adhesive.

The polythiol is normally present in a concentration of up to about 10% by weight preferably from 0.3 to about 6% by weight more preferably from about 0.3 to about 1% by weight based on a total weight of the pressure-sensitive adhesive rubber and total functional polythiol.

A variety of polythiols can be used, including pentaerythritoltetrathiolglycolate, pentaerythritoltetra(3-mercaptopropionate), trimethylolethanetrimercaptopropionate, trimethylolpropanetrithioglycolate, trimethylolpropanetri(3-mercaptopropionate) and mixtures thereof. The presently preferred rubber-based pressure-sensitive adhesive comprises a tackified mixture of styrene-butadiene-styrene block copolymer and a styrene-butadiene block copolymer.

As indicated, cure may be achieved by electron-beam (EB) and/or ultraviolet (UV) radiation. Where electron-beam cure is employed, dosage levels may range from about 10 to about 100 kiloGray (kGy). A photoinitiator is required for UV curing.

As compared to multifunctional acrylates and methacrylates, such polythiol required to achieve the significant increase in high-temperature shear is less and there is a lesser adverse affect on ambient temperature properties such as 180° peel and loop tack.

BRIEF DESCRIPTION OF THE DRAWINGS

The attached figures graphically illustrate the benefit of using the polythiols of the instant invention. FIG. 1 graphically shows the effect of using various dosages of electron-beam radiation in the absence of a polythiol or multifunctional acrylate.

FIG. 2 shows the effect of using 5.3% of TMPTG, a multifunctional polythiol. While elevated temperature shear is significantly increased, there is a relatively minimal loss in 180° peel and loop tack at ambient temperature. FIG. 3 shows, by contrast, the use of 5.3% PETA (pentaerythritoltriacrylate) which results in a substantially greater loss in 180° peel and loop tack. The percentages of losses or gains of FIGS. 1, 2 and 3 are shown in FIGS. 17 and 18.

The effect of reducing the level of PETA to 1.25% by weight is depicted in FIG. There occurs less of a loss in ambient temperature properties of 180° peel and loop tack. The dosage requirements are increased substantially to achieve a significant increase in elevated temperature shear.

FIG. 5 shows the ability to reduce TMPTG levels to as low as 0.3% by weight and achieve an excellent improvement in elevated temperature shear with minimal loss of ambient temperature properties.

FIGS. 6 - 13 graphically illustrate the ability to use TMPTG for solvent-coating operations where the solvent must be evaporated at some elevated temperature. At TMPTG concentrations of 0.3 or0.63% by weight, elevated temperature properties are improved with minimal change in 180° peel, room temperature shear and loop tack for the more severe SAFT test as described herein.

It will be noted here that the higher concentration of TMPTG had the greatest effect on improving adhesive properties. But still, a major improvement was achieved at less than 1% by weight TMPTG.

FIGS. 14-16 are for another adhesive system showing the effect of the polythiol on 180° peel, loop tack and 70° C. shear as a function of EB dosage.

FIGS. 17 and 18 plot the percent change in 180° peel and loop tack for 0 crosslinker 5.3% TMPTG and 5.3% PETA to show a much greater loss in these properties with PETA as used when compared to TMPTG. The sources are Tables I, II, and III.

DETAILED DESCRIPTION

According to the present invention, there is provided radiation-cured rubber-based (elastomer) pressure-sensitive adhesives having enhanced elevated temperature properties, in particular elevated temperature shear coupled with excellent adhesion to low and high energy substrates at ambient temperature.

The improvement is realized by irradiating rubber-based pressure-sensitive adhesives, particularly those based on di- and/or tri-block copolymers in which is employed as a crosslinking agent at least one functional polythiol. Improvements in high-temperature shear as compared to other crosslinking materials such as multi-functional acrylates and methacrylates are such that a greater increase in elevated temperature properties can be realized with less crosslinking agents with a lesser reduction in ambient temperature adhesive properties. The utility of products formed in accordance with the invention includes high-temperature duct tapes, transfer tapes, labels and the like.

The pressure-sensitive rubber-based adhesives useful in the practice of the instant invention may be formulated as hot-melt adhesives, solvent adhesives, emulsion adhesives and the like, with hot-melt or solvent-based adhesives presently being preferred.

Pressure-sensitive adhesives employed are normally based on di-block and tri-block copolymers and mixtures thereof. Responsive natural rubbers and non-curing resin modified elastomers may also be used. Suitable rubbers for improvement are described, for instance, in U.S. Pat. Nos. 3,239,478 to Harlan; 4,152,231 to St. Clair et al; 3,676,202 to Korpman; 3,723,170 to Korpman; 3,783,072 to Korpman; 3,932,328 to Korpman; and 4,028,292 to Korpman, each incorporated herein by this reference.

It is presently preferred that the rubber-based pressure-sensitive adhesive compositions enhanced in accordance with the instant invention be styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-butadiene and styrene-isoprene block copolymers, such as the Kraton resins manufactured and sold by Shell Chemical Company.

The polythiols used to enhance the high-temperature properties of the rubber-based pressure-sensitive adhesive may vary widely. We have found that polythiols in which the thiol group is connected to the balance of the polymer chain through an ester linkage are particularly effective.

While no use limiting the functional polythiols which may be used therein mentioned includes pentaerythritoltetrathioglycolate (PETTG), dipentaerythritoltetra(3-mercaptopropionate),pentaerythritoltetra(3-mercaptopropionate) (PETMP), trimethylolethanetrimercaptopropionate (TMETMP), trimethylolpropanetrithioglycolate (TMPTG), glycoldimercaptoacetate;2,2,dimercaptodiethylether, polyethyleneglycoldimercaptoacetate, polyethyleneglycol(3-mercaptopropionate, trimethyloltri(3-mercaptopropionate),trimethylolpropanetri(3-mercaptopropionate) (TMFTMP)and the like. Trimethylolpropanetri(3-mercaptopropionate) is presently preferred. Polythiol concentrate can range from up to about 10% by weight or more of the rubber preferably from about 0.3 to about 0.6% by weight based on the total weight of the rubber and more preferably from about 0.1 to about 1% by weight. Remarkable results can be obtained in a concentration of less than 1% polythiol.

When electron-beam (EB) is employed as the energy source to increase high-temperature properties, the normal levels may range from about 1 to about 100 kiloGray (kGy) preferably from about 10 to about 50 kGy. An alternative which may be used is ultraviolet radiation. UV irradiation requires the use of a photoinitiator and may be employed in conjunction with EB radiation.

When employing resin modification of a pressure-sensitive adhesive, it is preferred to employ non-curing resins as resins which undergo cure will diminish the improvement in high-temperature properties realized in accordance with the instant invention. In operation, the pressure-sensitive adhesive is normally cast onto a substrate, either face material or release layer, and is subjected to radiation cure (EB, UV or a combination of the two). Cure may be open face, i.e. exposure directly to the surface of the adhesive or through an energy transparent surface such as Mylar. Cure may be of a composite stock, i.e. face material, adhesive and release liner, or in a configuration when after curing, the pressure-sensitive adhesive and face material is wound into a roll or tape.

The particular benefit of using the polythiols of the instant invention is that less agent and energy are used to achieve the same degree of elevated temperature shear properties with minimal reduction in ambient temperature properties as compared with other multifunctional monomers such as multifunctional acrylates and methacrylates.

The following is illustrative of the Examples and Controls provided in accordance with the instant invention.

In the following Examples and Controls, shear was determined by ASTMD-3654-78 and D-1000-60 and PSTC (Pressure-Sensitive Tape Council) Test #7, 6th Ed.; Looptack by PSTC Test #7, 6th Ed.

Shear Adhesion Failure Temperature (SAFT) is determined by first heat-bonding aluminum plates overlapped to a bond area of one square inch. The bonded plates are heated to 70° C. and maintained at that temperature for 12 hours. After cooling to ambient temperature, they are placed under a kilogram shear load and temperature raised at the rate of 60° C./hr. The temperature at which bond failure occurs is reported.

For the following Examples and Controls, there were employed as rubber-based pressure-sensitive adhesives:

    ______________________________________                                         % by Wgt.        Component                                                     ______________________________________                                         Base Adhesive A                                                                19.3             SBS linear copolymer                                                           containing about                                                               31% styrene                                                   16.1             SB copolymer                                                  25.8             Alpha pinene                                                                   tackifier                                                     32.3             Rosin ester tackifier                                          6.4             Compatible aromatic                                                            liquid resin                                                  Base Adhesive B                                                                38               SIS radial copolymer                                          50               Aliphatic hydrocarbon                                                          tackifier                                                     12               Liquid aliphatic                                                               hydrocarbon tackifier                                         ______________________________________                                          Note: Both contained antioxidants.                                       

Note: Both contained antioxidants.

EXAMPLE 1 AND CONTROLS 1 TO 3

The Base Adhesive A of Table I was mixed with 5.3% by weight trimethylolpropane trithioglycolate (TMPTG) and coated to a level of about 50± grams meter squared onto a substrate and dried at 70° C. for 15 minutes. The coating samples were laminated to Mylar and EB radiated through Mylar at the dosage levels shown in Tables I to IV.

Tables I and II show the relative performance of the composition with and without addition of TMPTG. Table III, serving as a control, illustrates that while pentaerythritoltriacrylate (PETA) can also improve elevated temperature performance, there is a material sacrifice of ambient temperature properties particularly loop tack. FIGS. 1, 2 and 3 graphically display the differences.

When the concentration of PETA was reduced by 1.25% by weight, where there was a significant loss in peel and loop tack with the most significant loss in loop tack, there was a lesser improvement in elevated temperature shear establishing that the effectiveness of PETA was dropping off. This is shown in Table III and graphically depicted in FIG. 4.

By contrast, in utilizing 1.25% TMPTG, and as shown in Table IV, elevated temperature shear was still in excess of 86.4 kiloseconds and the level of elevated temperature shear was significantly unchanged when maintained at 70° C. over a period of 8 weeks. It was evident that TMPTG was dramatically and unexpectedly superior to PETA in the ability to achieve improved elevated temperature properties at minimal concentration with minimal adverse affect on ambient temperature properties of 180° peel and loop tack at ambient temperature.

                  TABLE I                                                          ______________________________________                                         (Control 1)                                                                    No Crosslinking Additive                                                       EB Dosage, kGy                                                                              0        30       50     80                                       ______________________________________                                         180° Peel, kN/m                                                                      1.6(p)   1.5(p)   1.2(p) 1.2(p)                                   Looptack, kN/m                                                                              2.8(p)   3.0(p)   2.4(p) 1.7(p)                                   Shear at 70° C.*,ks                                                                   1.02(c)  0.86(c)  0.63(c)                                                                              2.8(c)                                   ______________________________________                                    

                  TABLE II                                                         ______________________________________                                         (Example 1)                                                                    Crosslinking Additive - 5.3% by wgt TMPTG                                      EB Dosage, kGy                                                                            0       30        50      80                                        ______________________________________                                         180° Peel, kN/m                                                                    .sup. 1.7(ps)                                                                          1.3(ps)   1.3(ps) 1.2(ps)                                   Looptack, kN/m                                                                            2.5(p)  2.0(p).sup.                                                                              1.9(p).sup.                                                                            1.8(p).sup.                               70° C. ETS, ks                                                                     0.8(c)  86.4 + (nc)                                                                              86.4 + (nc)                                                                            86.4 + (nc)                               ______________________________________                                    

                  TABLE III                                                        ______________________________________                                         (Control 2)                                                                    Crosslinking Additive - 5.3% by wgt PETA                                       EB Dosage, kGy 30        50        80                                          ______________________________________                                         180° Peel, kN/m                                                                    1.5(ps) 0.95(ps)  0.99(ps)                                                                               0.90(ps)                                  Looptack, kN/m                                                                            2.3(p)  1.3(p) .sup.                                                                             1.4(p) .sup.                                                                           1.3(p) .sup.                              70° C. ETS, ks                                                                     4.7(c)  86.4 + (nc)                                                                              86.4 + (nc)                                                                            86.4 + (nc)                               ______________________________________                                    

                  TABLE IV                                                         ______________________________________                                         (Control 3)                                                                    Crosslinking Additive - 1.25% by wgt PETA                                      EB Dosage, kGy                                                                             0       30        50     80                                        ______________________________________                                         180° Peel, kN/m                                                                     .sup. 1.2(ps)                                                                          .sup. 1.3(ps)                                                                             1.2(ps)                                                                               1.1(ps)                                  Looptack, kN/m                                                                             1.7(p)  1.8(p)     1.7(p)                                                                                1.7(p)                                   70° C. ETS, ks                                                                      4.7     6.8(p)    24.7(p)                                                                               63. (p)                                   ______________________________________                                          ks = kiloseconds                                                               ETS = Elevated Temperature Shear                                               p = panel failure                                                              c = cohesive failure                                                           ps =panel stain                                                                nc = no creep                                                                  + = greater than                                                               kN = kilo newtons/meter                                                        *70° C. ETS                                                       

EXAMPLE 2

The data is shown in Table V and graphically illustrated in FIG. 5 establishing that using the Base Adhesive A elevated temperature shear at 50 kGy was quite high for a TMPTG concentration of only 0.3% by weight of the composition. The dramatic improvement in elevated temperature shear was realized with even less affect on room temperature properties, particularly loop tack.

                  TABLE V                                                          ______________________________________                                         Dosage TMPTG      180° Peel                                                                         Loop Tack,                                                                             70° C. ETS,                         kGy    Con.Wgt %  RT, kN/m  kN/m    ks, 500 g                                  ______________________________________                                          0     0          1.6(p).sup.                                                                              2.3(p)  0.77(c)                                    50     0.3        1.3(ps)   2.2(p)  86.4 + (nc)                                ______________________________________                                    

EXAMPLE 3

The following study, graphically illustrated in FIGS. 6 to 13, was to establish that the use of TMPTG to enhance properties is unaffected by solvent coating of the base adhesive. In each, there is shown the TMPTG concentration and whether the cast adhesive had been heated to 200° or to 250° during the solvent removal process at the TMPTG levels shown.

With respect to FIGS. 6 and 7, concerning the property of 180° peel adhesion, the lesser amount of TMPTG caused the least reduction in 180° peel adhesion and even matched low-temperature adhesion at a dosage of 10 kGy.

With respect to FIG. 7, increasing TMPTG concentration to 0.63% by weight TMPTG with all other factors being the same resulted in some loss in 180° peel adhesion, but again the amount was negligible.

As shown in FIGS. 8 and 9, there was a marked improvement in room temperature shear dosages from 10 to 50 kGy as compared to compositions to which no TMPTG had been added.

FIGS. 10 and 11 establish loop tack and gave comparable results where both 0.3% TMPTG and 0.63% TMPTG.

As shown in FIGS. 12 and 13, for the more strenuous SAFT tests the higher concentration of TMPTG, mainly 0.63% by weight, appeared to have a pronounced improvement in time resistance to failure as compared to the lower level of 0.3% by weight TMPTG. It should be noted, however, that PETA at the levels employed would not provide any significant improvement.

EXAMPLES 4 TO 15 AND CONTROL 4

The following Examples illustrate the affect of other polythiols on Shear Adhesion Failure Temperature (SAFT) and 70° C. and room and elevated temperature shear.

    ______________________________________                                         Ex-                        SAFT    70° C.                                                                        RT                                    ample/             EB      1 kg/n.sup.2 @                                                                         Shear Shear                                 Control                                                                               Polythiol   Dosage  1° C./min.                                                                      ks    ks                                    ______________________________________                                         Cont. 4                                                                               0           --      82.2° C.                                                                        2.6(c)                                                                               216+                                  Ex. 4  0.3 TMPTG   25       87                                                 Ex. 5  0.3 TMPTG   50       85                                                 Ex. 6  0.5 TMPTG   25      125                                                 Ex. 7  0.5 TMPTG   50      135                                                 Ex. 8  0.8 TMPTG   25      131     216+  684+                                  Ex. 9  0.8 TMPTG   50      140     216+  684+                                  Ex. 10 0.8 PETTG   25      131     216+  684+                                  Ex. 11 0.8 PETTG   50      160     216+  684+                                  Ex. 12 0.8 PETMP   25      126     216+  684+                                  Ex. 13 0.8 PETMP   50      160     216+  684+                                  Ex. 14 0.8 TMETMP  25      125     216+  684+                                  Ex. 15 0.8 TMETMP  50      159     216+  684+                                  ______________________________________                                          RT = room temperature                                                    

EXAMPLES 16 AND 7 AND CONTROLS 5 AND 6

Base Adhesive B was used for Examples 6 and 7 there was added 1% by weight TMPTG. For instance, the adhesive was hot-melt coated onto a substrate (Mylar for Example 6 and Control 4 and aluminum for Example 17 and Control 6) to a coating level of 50 grams per sq. m. Controls 5 and 6 show adhesive performance at 0 kGy while Examples 16 and 17 show adhesive performance after dosage to levels of 30, 50 and 70 kGy. The results are tabulated in Tables VI and VII, and for Table VI depicted in FIGS. 14, 15 and 16.

                  TABLE VI                                                         ______________________________________                                         EB Dosage, kGy                                                                            0        30        50      70                                       ______________________________________                                         180° Peel, kN/m                                                                     1.0      1.14      1.16    1.06                                    Looptack, kN/m                                                                             1.50(p)  1.42(p)   1.50(p)                                                                                1.46(p)                                 RTS(a), ks 171.7    171.7     171.7    9(p)                                    70° C. ETS, ks                                                                      0.4(c)   2.6(p/c)  27.5(p/c)                                                                             33(p/c)                                  ______________________________________                                    

                  TABLE VII                                                        ______________________________________                                         EB Dosage, kGy                                                                            0        30       50      80                                        ______________________________________                                         180° Peel, kN/m                                                                    1.36      1.48     1.39    1.35                                     70° C. ETS(a), ks                                                                  0.98     38.3(c)  177(f/c)                                                                               163(f/p)                                  ______________________________________                                          a = 1 kg load                                                                  f = face stock failure                                                   

EXAMPLE 18

Using Base Adhesive A, TMPTG was compared to TMPTMP as a polythiol crosslinker at concentrations of up to 1% by weight. Table VIII shows the initial performance of the EB-cured composition, while Table IX shows the change for the composition cured at a dosage of 50 kGy for the time and temperature shown.

                  TABLE VIII                                                       ______________________________________                                         CROSS-                                                                         LINKER  TMPTG    TMTMP    TMTMP  TMTMP  TMTMP                                  LEVEL:  0.3%     0.4%     0.6%   0.8%   1.0%                                   ______________________________________                                         S.A.F.T. (°C.)                                                          30 kGy  101       87      84      86    93                                     40 kGy  122      100      94     101    93                                     50 kGy  141      106      108    111    128                                    180° SS Peel (kN/m)                                                     30 kGy  2.03     2.22     2.33   2.19   2.05                                   40 kGy  1.92     2.19     2.22   2.08   2.05                                   50 kGy  1.94     2.19     2.10   2.08   2.05                                   180° PP Peel (kN/m)                                                     30 kGy  1.40     1.59     1.65   1.35   1.44                                   40 kGy  1.14     1.68     1.58   1.40   1.21                                   50 kGy  1.26     1.66     1.44   1.28   1.12                                   ______________________________________                                          SS = stainless steel                                                           PP = polypropylene                                                       

                  TABLE IX                                                         ______________________________________                                         CROSS-                                                                         LINKER: TMPTG    TMTMP    TMTMP  TMTMP  TMTMP                                  LEVEL:  0.3%     0.4%     0.6%   0.8%   1.0%                                   ______________________________________                                         S.A.F.T. (°C.)                                                          Initial 141      106      108    111    128                                    2 Wk. @ 127      118      124    118    115                                    50° C.                                                                  4 Wk. @ 144      125      113    127    139                                    50° C.                                                                  180° SS Peel (kN/m)                                                     Initial 1.94     2.19     2.10   2.08   2.00                                   2 Wk. @ 1.65     1.79     1.75   1.68   1.70                                   RT                                                                             2 Wk. @ 1.79     1.86     1.87   1.84   1.75                                   50° C.                                                                  4 Wk. @ 1.94     2.05     2.01   2.05   1.98                                   RT                                                                             4 Wk. @ 2.08     2.19     2.26   2.05   2.03                                   50° C.                                                                  ______________________________________                                    

EXAMPLES 19 to 26 and Control 8

To 100 parts by weight of Base Adhesive A there was added 1 part by weight photoinitiator Irgacure 651, manufactured and sold by Ciba-Geigy Co., and 0.6 parts by weight TMPTG. The mix was knife-coated onto a release surface and dried at 70° C. for 20 minutes to the coating weight shown in Table X. The ultraviolet lamps used were 80 watts/cm with surface exposure being dependant on web speed.

                                      TABLE X                                      __________________________________________________________________________           Ct.Wt.                           Loop                                                                               E.T.Shear                           Example/                                                                             (g/m.sup.2)                                                                        Web Speed                                                                             U.V.Dose                                                                             EB dosage                                                                            Face 180° Peel                                                                    Tack                                                                               (70° C.) ks                  Control                                                                              60  (ft/min.lamp)                                                                         kj/m.sup.2                                                                           (kGy) Exposure                                                                            (n/m)                                                                               (n/m)                                                                              2.68(c)                             __________________________________________________________________________     Cont. 8                                                                              60  Infinity                                                                              0     --    Open 2.32(p)                                                                             --  2.68(c)                                                          Face                                              Ex. 19                                                                               60  20     5.8   --         1.72(p)                                                                             1.74(ss)                                                                           592 + (nc)                          Ex. 20                                                                               60  40     2.4   --         1.76(p)                                                                             1.74(ss)                                                                           276 + (nc)                          Ex. 21                                                                               60  60     1.6   --         2.02(p)                                                                             2.57(ss)                                                                           1.4(f)                              Ex. 22                                                                               60  75     1.4   --         1.74(p)                                                                             1.47                                                                               4.16(b)                             Ex. 23                                                                               60  100    1.0   --         1.77 2.02(ss)                                                                           276 + (nc)                          Ex. 24                                                                               44  20     5.8   --    Thru 1.05(p)                                                                             8.24(ss)                                                                           1.4(f)                                                           Mylar                                             Ex. 25                                                                               44  60     1.6   --         1.42(p)                                                                             2.37(p)                                                                            1.4(f)                              Ex. 26                                                                               44  75     1.4   50         1.31(p)                                                                             1.38(ss)                                                                           2.8(f/p)                            __________________________________________________________________________      c = cohesive failure                                                           b = 1 kg load                                                                  ss =  slipstick                                                                kj/m.sup.2 = kilojoules/m.sup.2                                           

What is claimed is:
 1. A cured rubber-based pressure-sensitive adhesive which comprises a tackified elastomeric rubber-based pressure sensitive adhesive crosslinked with a polythiol crosslinking agent present in an amount sufficient to provide upon exposure to electron-beam radiation or ultraviolet radiation in the further presence of a photo-initiator, an 70° C. shear of at least about 2.6 kiloseconds while providing ambient temperature loop tack of at least about 1.8 kN/m and 180° peel of at least 1.2 kN/m at a coat weight of about 50 g/m².
 2. A cured rubber-based pressure sensitive adhesive as claimed in claim 1 in which the polythiol is present in a concentration of from 0.3 to about 6% by weight based on a total weight of the rubber-based pressure-sensitive adhesive rubber and the polythiol.
 3. A cured rubber-based pressure-sensitive adhesive as claimed in claim 1 in which the rubber-based pressure-sensitive adhesive comprises a di-block copolymer, a tri-block copolymer or mixtures thereof.
 4. A rubber-based pressure-sensitive adhesive as claimed in claim 1 in which the rubber-based pressure-sensitive adhesive comprises a styrene-butadiene-styrene block copolymer and in which in 70° C. shear is in excess of 86.4 kiloseconds.
 5. A radiation cured rubber-based pressure-sensitive adhesive which comprises a tackified elastomeric rubber-based pressure-sensitive adhesive selected from the group consisting of styrene-isoprene, styrene butadiene, styrene isoprene styrene, styrene-butadiene styrene block copolymers and mixtures thereof, and crosslinked with a polythiol crosslinking agent present in a positive amount of up to about 10% by weight based on the weight of the rubber-based pressure-sensitive adhesive and polythiol, to provide a cured pressure-sensitive adhesive having ambient temperature loop tack of at least about 1.8 kN/m and a 180° peel of at least about 1.2 kN/m and a 70° C. shear of about at least 2.6 kiloseconds at a coat weight of about 50 g/m².
 6. A cured rubber-based pressure-sensitive adhesive as claimed in claim 3 in which the polythiol crosslinking agent is selected from the group consisting of pentaerythritoltetrathiolglycolate, pentaerythritoltetra(3-mercaptopropionate), trimethylolethanetrimercaptopropionate, trimethylolpropanetrithioglycolate, trimethylolpropanetri(3-mercaptopropionate), and mixtures thereof.
 7. A cured rubber-based pressure-sensitive adhesive as claimed in claim 6 in which the polythiol is present in a concentration of from about 0.3 to about 1% by weight based on a total weight of the rubber-based pressure-sensitive adhesive and the polythiol.
 8. A cured rubber-based pressure-sensitive adhesive as claimed in claim 6 in which the rubber-based pressure-sensitive adhesive comprises a di-block copolymer, a tri-block copolymer or mixtures thereof.
 9. A cured rubber-based pressure-sensitive adhesive as claimed in claim 6 in which the rubber-based pressure-sensitive adhesive comprises a styrene-butadiene-styrene block copolymer and in which 70° C. shear is in excess of 86.4 kiloseconds.
 10. A cured rubber-based pressure-sensitive adhesive as claimed in claim 5 in which the polythiol is present in a concentration of from about 0.3 to about 1% by weight based on a total weight of the rubber-based pressure-sensitive adhesive and the polythiol.
 11. A cured rubber-based pressure-sensitive adhesive as claimed in claim 5 in which the rubber-based pressure-sensitive adhesive comprises a di-block copolymer, a tri-block copolymer or mixtures thereof.
 12. A radiation-cured rubber-based pressure-sensitive adhesive which comprises at least one tackified elastomeric rubber-based pressure-sensitive adhesive cured by electron-beam radiation at a level up to about 100 kGy in the presence of a functional polythiol crosslinking agent present in an amount up to about 10% by weight based on the weight of the pressure-sensitive adhesive and the polythiol, said cured pressure-sensitive adhesive having an ambient temperature loop tack of at least 1.8 kN/m and a 180° peel of at least about 1.2 kN/m and an 70° C. shear of at least about 2.6 kiloseconds at a coat weight of about 50 g/m².
 13. A radiation-cured pressure-sensitive adhesive as claimed in claim 12 in which the functional polythiol is selected from the group consisting of pentaerythritoltetrathiolglycolate, pentaerythritoltetra(3-mercaptopropionate), trimethylolethanetrimercaptopropionate, trimethylolpropanetrithioglycolate, trimethylolpropanetri(3-mercaptopropionate), and mixtures thereof.
 14. A radiation-cured rubber-based pressure sensitive adhesive as claimed in claim 12 in which the rubber-based pressure-sensitive adhesive comprises a di-block copolymer, a tri-block copolymer, or mixtures thereof.
 15. A radiation-cured rubber-based pressure-sensitive adhesive as claimed in claim 12 in which the rubber-based pressure-sensitive adhesive comprises a styrene-butadiene-styrene block copolymer and in which 70° C. shear is in excess of 86.4 kiloseconds.
 16. A radiation-cured pressure-sensitive adhesive as claimed in claim 15 in which the functional polythiol is selected from the group consisting of pentaerythritoltetrathiolglycolate, pentaerythritoltetra(3-mercaptopropionate), trimethylolethanetrimercaptopropionate, trimethylolpropanetrithioglycolate, trimethylolpropanetri(3-mercaptopropionate), and mixtures thereof.
 17. A radiation-cured rubber-based pressure-sensitive adhesive as claimed in claim 12 in which the polythiol is present in a concentration of from 0.3 to about 6% by weight based on a total weight of the pressure-sensitive adhesive rubber and polythiol.
 18. A radiation-cured rubber-based pressure-sensitive adhesive as claimed in claim 12 in which the polythiol is present in a concentration of from about 0.3 to about 1% by weight based on a total weight of the pressure-sensitive adhesive and the polythiol.
 19. A radiation-cured rubber-based pressure-sensitive adhesive as claimed in claim 13 in which the rubber-based pressure-sensitive adhesive comprises a di-block copolymer, a tri-block copolymer, or mixtures thereof.
 20. A radiation-cured rubber-based pressure-sensitive adhesive as claimed in claim 13 in which the rubber-based pressure-sensitive adhesive comprises a styrene-butadiene-styrene block copolymer and in which the 70° C. shear is at least 86.4 kiloseconds.
 21. A radiation-cured rubber-based pressure-sensitive adhesive which comprises a tackified elastomeric rubber-based pressure-sensitive adhesive cured by ultraviolet radiation in the presence of a photo-initiator and a functional polythiol crosslinking agent present in an amount up to about 10% by weight based on the weight of the rubber-based pressure-sensitive adhesive and polythiol, said cured pressure-sensitive adhesive having an ambient temperature loop tack of at least 0.9 kN/m of 180° peel of at least 1 kN/m and an 70° C. shear of at least about 4 kiloseconds at a coat weight of about 44 g/m².
 22. A radiation-cured pressure-sensitive adhesive as claimed in claim 21 in which the functional polythiol crosslinking agent is selected from the group consisting of pentaerythritoltetrathiolglycolate, pentaerythritoltetra(3-mercaptopropionate), trimethylolethanetrimercaptopropionate, trimethylolpropanetrithioglycolate, trimethylolpropanetri(3-mercaptopropionate), and mixtures thereof.
 23. A radiation-cured rubber-based pressure-sensitive adhesive as claimed in claim 22 in which the rubber-based pressure-sensitive adhesive comprises a styrene-butadiene-styrene block copolymer and in which 70° C. shear is in excess of 86.4 kiloseconds.
 24. A radiation-cured rubber-based pressure-sensitive adhesive as claimed in claim 21 in which the rubber-based pressure-sensitive adhesive comprises a di-block copolymer, a tri-block copolymer, or mixtures thereof.
 25. A radiation-cured rubber-based pressure-sensitive adhesive as claimed in claim 21 in which the rubber-based pressure-sensitive adhesive comprises a styrene-butadiene-styrene block copolymer and in which 70° C. shear is in excess of 86.4 kiloseconds.
 26. A radiation-cured rubber-based pressure-sensitive adhesive as claimed in claim 21 in which the polythiol is present in a concentration of from 0.3 to about 6% by weight based on a total weight of the pressure-sensitive adhesive rubber and the polythiol.
 27. A radiation-cured rubber-based pressure-sensitive adhesive as claimed in claim 21 in which the polythiol is present in a concentration of from about 0.3 to about 1% by weight based on a total weight of the pressure-sensitive adhesive and the polythiol.
 28. A process for improving the high-temperature properties of rubber-based pressure-sensitive adhesives which comprises subjecting a rubber-based pressure-sensitive adhesive, comprising the action of electron-beam radiation, in the presence of a polythiol crosslinking agent, said polythiol being present in an amount up to about 10% by weight based on the weight of the pressure-sensitive adhesive, at a dosage level sufficient to increase high-temperature shear of the pressure-sensitive adhesive.
 29. A process as claimed in claim 28 in which the electron-beam radiation dosage level is from about 10 to 100 kiloGray.
 30. A process as claimed in claim 29 in which the functional polythiol crosslinking agent is selected from the group consisting of pentaerythritoltetrathiolglycolate, pentaerythritoltetra(3-mercaptopropionate), trimethylolethanetrimercaptopropionate, trimethylolpropanetrithioglycolate, trimethylolpropanetri(3-mercaptopropionate), and mixtures thereof.
 31. A process as claimed in claim 29 in which the polythiol is present in a concentration of from about 0.3 to about 1% by weight based on a total weight of the pressure-sensitive adhesive and the polythiol.
 32. A process as claimed in claim 28 in which the level of exposure is from about 10 to about 50 kiloGray.
 33. A process as claimed in claim 32 in which the functional polythiol crosslinking agent is selected from the group consisting of pentaerythritoltetrathiolglycolate, pentaerythritoltetra(3-mercaptopropionate), trimethylolethanetrimercaptopropionate, trimethylolpropanetrithioglycolate, trimethylolpropanetri(3-mercaptopropionate), and mixtures thereof.
 34. A process as claimed in claim 33 in which the polythiol is present in a concentration of from about 0.3 to about 1% by weight based on a total weight of the pressure-sensitive adhesive and the polythiol.
 35. A process as claimed in claim 28 in which the functional polythiol crosslinking agent is selected from the group consisting of pentaerythritoltetrathiolglycolate, pentaerythritoltetra(3-mercaptopropionate), trimethylolethanetrimercaptopropionate, trimethylolpropanetrithioglycolate, trimethylolpropanetri(3-mercaptopropionate), and mixtures thereof.
 36. A process as claimed in claim 35 in which the polythiol is present in a concentration of from about 0.3 to about 6% by weight based on a total weight of the pressure-sensitive adhesive rubber and the polythiol.
 37. A process as claimed in claim 28 in which the polythiol is present in a concentration of from about 0.3 to about 6% by weight based on a total weight of the pressure-sensitive adhesive rubber and the polythiol.
 38. A process as claimed in claim 28 in which the polythiol is present in a concentration of from about 0.3 to about 1% by weight based on a total weight of the pressure-sensitive adhesive and the polythiol.
 39. A process as claimed in claim 38 in which the polythiol is present in a concentration of from about 0.3 to about 1% by weight based on a total weight of the pressure-sensitive adhesive and the polythiol.
 40. A process as claimed in claim 28 in which the pressure-sensitive adhesive comprises a styrene-butadiene-styrene block copolymer and in which 70° C. shear is in excess of 86.4 kiloseconds.
 41. A process for improving the high-temperature properties of rubber-based pressure-sensitive adhesives which comprises subjecting a tackified rubber-based pressure-sensitive adhesive, to the action of ultraviolet radiation, in the presence of a photo-initiator and polythiol crosslinking agent, present in an amount up to about 10% by weight based on the weight of the pressure-sensitive adhesive, at a dosage level sufficient to provide a pressure-sensitive adhesive having an ambient temperature loop tack of about 1.8 kN/m, a 180° peel of at least about 1.2 kN/m and a 70° C. shear of at least about 2.6 kiloseconds at a coat weight of about 44 g/m².
 42. A process as claimed in claim 41 in which the polyfunctional thiol is selected from the group consisting of pentaerythritoltetrathiolglycolate, pentaerythritoltetra(3-mercaptopropionate), trimethylolethanetrimercaptopropionate, trimethylolpropanetrithioglycolate, trimethylolpropanetri(3-mercaptopropionate), and mixtures thereof.
 43. A process as claimed in claim 42 in which the polythiol is present in a concentration of from about 0.3 to about 1% by weight based on a total weight of the pressure-sensitive adhesive and the polythiol.
 44. A process as claimed in claim 42 in which the polythiol is present in a concentration of from about 0.3 to about 6% by weight based on a total weight of the pressure-sensitive adhesive and the polythiol.
 45. A process as claimed in claim 41 in which the polythiol is present in a concentration of from about 0.3 to about 6% by weight based on a total weight of the pressure-sensitive adhesive and the polythiol.
 46. A process as claimed in claim 41 in which the polythiol is present in a concentration of from about 0.3 to about 1% by weight based on a total weight of the pressure-sensitive adhesive and the polythiol.
 47. A cured rubber-based pressure-sensitive adhesive which comprises a tackified elastomeric rubber-based pressure-sensitive adhesive cured in the presence of a polythiol crosslinking agent present in an amount sufficient to provide upon cure a shear adhesion failure temperature of at least 85° C. at a coat weight of 50 g/m².
 48. A cured rubber-based pressure-sensitive adhesive which comprises a tackified elastomeric rubber-based pressure-sensitive adhesive cured in the presence of a polythiol crosslinking agent, said cured pressure-sensitive adhesive providing an ambient temperature loop tack of at least about 1.8 kN/m and 180° peel of at least 1.4 kN/m and a 70° C. shear of at least 2.8 kiloseconds at a coat weight of 50 g/m². 